Using the Electrochemistry of the Electrospray Ion Source

Berkel, Gary J. Van; Kertész, Vilmos

doi:10.1021/ac071944a

Cited by 172 publications

(208 citation statements)

References 49 publications

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“…The spraying current is a key parameter in the electrochemical processes involved in electrospray ionization [36,[41][42][43]. Thus, before investigating the pH profiles of the spray plume with exposure to basic vapors, we first address the effect of basic vapors on the spraying current.…”

Section: Resultsmentioning

confidence: 99%

“…We postulate that similar physicochemical properties are obtained for water droplets seeded with other amines (e.g., triethylamine and piperidine), though solubility and conductivity are available only for triethylamine [49][50][51]. The spraying current is a key parameter for electrochemical processes occurring in electrospray and plays a central role in the pH changes observed at the exit of the emitter tip, before the generation of the spray plume [36,[41][42][43]. Electrochemical events associated with electrospray ionization have been extensively investigated by Van Berkel's group and have been widely referenced in ESI mass spectrometry publications (for a review see References [41,52]).…”

Section: Effect Of Basic Vapors On the Spraying Current And Electrochmentioning

confidence: 87%

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Basic Vapor Exposure for Tuning the Charge State Distribution of Proteins in Negative Electrospray Ionization: Elucidation of Mechanisms by Fluorescence Spectroscopy

Girod

Antoine

Dugourd

et al. 2012

J. Am. Soc. Mass Spectrom.

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Manipulation for simplifying or increasing the observed charge state distributions of proteins can be highly desirable in mass spectrometry experiments. In the present work, we implemented a vapor introduction technique to an Agilent Jet Stream ESI (Agilent Technologies, Santa Clara, CA, USA) source. An apparatus was designed to allow for the enrichment of the nitrogen sheath gas with basic vapors. An optical setup, using laser-induced fluorescence and a pH-chromic dye, permits the pH profiling of the droplets as they evaporate in the electrospray plume. Mechanisms of pH droplet modification and its effect on the protein charging phenomenon are elucidated. An important finding is that the enrichment with basic vapors of the nitrogen sheath gas, which surrounds the nebulizer spray, leads to an increase in the spray current. This is attributed to an increase in the electrical conductivity of water-amine enriched solvent at the tip exit. Here, the increased current results in a generation of additional electrolytically produced OH -ions and a corresponding increase in the pH at the tip exit. Along the electrospray plume, the pH of the droplets increases due to both droplet evaporation and exposure to basic vapors from the seeded sheath gas. The pH evolution in the ESI plume obtained using pure and basic seeded sheath gas was correlated with the evolution of the charge state distribution observed in mass spectra of proteins, in the negative ion mode. Taking advantage of the Agilent Jet Stream source geometry, similar protein charge state distributions and ion intensities obtained with basic initial solutions, can be obtained using native solution conditions by seeding the heated sheath gas with basic vapors.

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Section: Resultsmentioning

confidence: 99%

Section: Effect Of Basic Vapors On the Spraying Current And Electrochmentioning

confidence: 87%

Basic Vapor Exposure for Tuning the Charge State Distribution of Proteins in Negative Electrospray Ionization: Elucidation of Mechanisms by Fluorescence Spectroscopy

Girod

Antoine

Dugourd

et al. 2012

J. Am. Soc. Mass Spectrom.

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“…Detailed inspection of the LC-FTMS data revealed that for some peptides the electrospray ionization generated not only common, multiply protonated peptides but also iron-cationized peptides due to iron cation-proton exchange in the steel electrospray needle (Van Berkel & Kertesz, 2007). This exchange was found to be more efficient under electrospray conditions than under nanospray conditions.…”

Section: Peptides From the Cfem Domain Are Capable Of Forming Iron Admentioning

confidence: 99%

Iron restriction-induced adaptations in the wall proteome of Candida albicans

et al. 2013

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The opportunistic fungal pathogen Candida albicans has developed various ways to overcome iron restriction in a mammalian host. Using different surface proteins, among them membrane-and wall-localized glycosylphosphatidylinositol (GPI) proteins, it can exploit iron from host haemoglobin, ferritin and transferrin. Culturing C. albicans in rich medium supplemented with the ferrous iron chelator bathophenanthroline disulfonic acid or in the minimal medium yeast nitrogen base resulted in a strong decrease of the iron content of the cells. MS analysis of the changes in the wall proteome of C. albicans upon iron restriction showed a strong increase in the levels of the GPI-modified adhesin Als3, which also serves as a ferritin receptor, and of the GPI-modified CFEM (common in fungal extracellular membranes) domain-containing proteins Csa1, Pga7, Pga10, and Rbt5. The wall levels of the GPI-modified proteins Hyr1, the adhesin Als4 and the copper-and zinc-containing superoxide dismutase Sod4 also strongly increased, whereas the levels of Tos1 (a non-GPI protein) and the GPI-modified adhesin Als2 strongly decreased. Strikingly, peptides derived from the CFEM domain of the haem-binding proteins Csa1, Pga10 and Rbt5 were capable of forming iron adduct ions during MS analysis, consistent with a key role of this domain in haem binding.

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“…ESI involves many redox reactions and can be considered as an electrochemical cell. [8] Indeed, in order to compensate the departure of an ion from the Taylor cone and to sustain the electrospray current heterogeneous electron-transfer reactions must occur at the conductive contact to the solution. Electrochemistry is thus inherent to the operation of the source and a better use of the electrochemistry involved in ESI is of interest to promote and detect specific molecules.…”

Section: Introductionmentioning

confidence: 99%

“…Electrochemistry is thus inherent to the operation of the source and a better use of the electrochemistry involved in ESI is of interest to promote and detect specific molecules. [8] The electrochemical reactions inherent to the ESI source take place at the working electrode in contact with the solution. The potential of the emitter electrode is not fixed during ESI-MS experiments and this potential is adjusted to a certain level depending on the current density, the concentration and redox potential of the analytes, and so forth.…”

Section: Introductionmentioning

confidence: 99%

About the Electrospray Ionization Source in Mass Spectrometry: Electrochemistry and On-chip Reactions

Prudent¹,

Méndez²,

Roussel³

et al. 2009

Chimia

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The present work shows that the electrochemical properties of electrospray ionization (ESI) can be used to add functions to the process. As example, we show how the choice of the electrode material can be used to study interactions between metal ions and biomolecules in mass spectrometry (MS). In positive ionization MS, an electrospray device acts as anode, which implies oxidation reactions. Sacrificial electrodes (made of copper or zinc) are used to supply the electrospray current and to produce cations that are able to react on-line with compounds of interest. Thus, the interactions between copper ions and ligands or peptides were investigated by using a copper electrode. Another example is the in situ electrogeneration of a dinuclear zinc(II) complex for the mass tagging of phosphopeptides when working with a zinc electrode. In order to perform these reactions on the same microchip, a dual-channel microsprayer was used, where one channel was dedicated to the tag electrogeneration and the other to the infusion of a phosphopeptides solution. Finally, this dual-channel microsprayer was used to study complexation at liquid-liquid interfaces in biphasic ESI-MS, such as thioether crowns and lead ions or peptides and phospholipids complexes. These examples illustrate the use of electrochemistry and on-chip reactions in ESI-MS analysis.

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Using the Electrochemistry of the Electrospray Ion Source

Cited by 172 publications

References 49 publications

Basic Vapor Exposure for Tuning the Charge State Distribution of Proteins in Negative Electrospray Ionization: Elucidation of Mechanisms by Fluorescence Spectroscopy

Basic Vapor Exposure for Tuning the Charge State Distribution of Proteins in Negative Electrospray Ionization: Elucidation of Mechanisms by Fluorescence Spectroscopy

Iron restriction-induced adaptations in the wall proteome of Candida albicans

About the Electrospray Ionization Source in Mass Spectrometry: Electrochemistry and On-chip Reactions

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